2-Arylaminonitrothiophenes as insecticides and acaricides

ABSTRACT

2-ARYLAMINONITROTHIOPHENES WHICH POSSESS ARTHROPODICIDAL, ESPECIALLY INSECTICIDAL OR ACARICIDAL, PROPERTIES. The compounds have the structure   IN WHICH X represents hydrogen, halogen or nitro, Y represents halogen, haloalkyl or nitro, Z represents halogen, cyano, nitro, lower alkyl, halo-lower alkyl, lower alkoxy, lower alkylsulphinyl, lower alkylsulphonyl, cycloalkyl, dialkylamino wherein each alkyl group contains up to six carbon atoms or amino wherein the nitrogen is part of a saturated heterocyclic ring, as in morpholino, and N IS AN INTEGER FROM 0 TO 5.

Unite States Patent [191 Buchel et al.

[ Sept. 9, 1975 2-ARYLAMINONITROTHIOPHENES AS INSECTICIDES ANDACARICIDES [75] Inventors: Karl Heinz B'lichel,

Wuppertal-Elberfeld; Ingeborg Hammann, Cologne, both of Germany [73]Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany [22] Filed: Apr. 12, 1974 [21] Appl. No.: 460,650

Related US. Application Data [62] Division of Scr. No. 74,917, Sept. 23,1970, Pat. No.

OTHER PUBLICATIONS Schuetz et 21]., Chem Ther. 1968, 3(4), pp. 289-295Open Sulfur l-leterocyclic Schaefer et a1., Ld. Eur. Biochem. Soc.Lett., 1970, 6(3), pp. 2l7220. Med. Chem. 2nd Ed. BurgerlntersciencePubl. Inc. New York 1960 pp. 72-74.

Chem. Abst. 48, 9354(a)1954.

Chem. Abst. 55, 2l09l(i)196l, and Chem. Abst. 61, 5593(b), (1964).

Primary ExaminerAlbert T. Meyers Assistant Examiner-D. W. RobinsonAttorney, Agent, or FirmBurgess, Dinklage & Sprung [57] ABSTRACT2-arylaminonitrothiophenes which possess arthropodicidal, especiallyinsecticidal or acaricidal, properties. The compounds have the structurein which X represents hydrogen, halogen or nitro,

Y represents halogen, haloalkyl or nitro,

Z represents halogen, cyano, nitro, lower alkyl, halo-lower alkyl, loweralkoxy, lower alkylsulphinyl, lower alkylsulphonyl, cycloalkyl,dialkylamino wherein each alkyl group contains up to six carbon atoms oramino wherein the nitrogen is part of a saturated heterocyclic ring, asin morpholino, and

n is an integer from 0 to 5.

11 Claims, No Drawings Z-ARYLAMINONITROTI-IIOPI-IENES AS INSECTICIDESAND ACARICIDES This is a division of application Ser. No. 74,917, filedSept. 23, 1970, now US. Pat. No. 3,839,359. 5

The present invention relates to certain new 2-arylaminonitrothiophenes,to a process for their preparation, and to their use as insecticides oracaricides.

It is known that 2,5-dibromo-3,4-dinitrothiophene exhibits fungicidaland insecticidal properties (cf. J apanese Pat. No. 19,733/64).Furthermore, 2,5-dichloro- 3,4-dinitrothiophene can be used as aninsecticidal agent (cf. U.S. Pat. No. 2,691,616). The insecticidalactivity of these previously known substances is, however, in many casesnot satisfactory.

The present invention provides 2-arylaminonitrothiophenes of the formulain which X represents hydrogen, halogen or nitro,

Y represents halogen, haloalkyl or nitro,

Z represents halogen, cyano, nitro, lower alkyl, halolowcr alkyl. loweralkoxy, lower alkylthio, lower alkylsulphinyl, lower alkylsulphonyl,cycloalkyl, dialkylamino wherein each alkyl group contains up to sixcarbon atoms or amino wherein the nitrogen is part of a saturatedheterocyclic ring, as in morpholino, and

n is an integer from 0 to 5.

The compounds exhibit very good insecticidal and acaricidal properties.

The invention also provides a process for the production of a2-arylaminonitrothiophene of the formula (I) in which a2-halonitrothiophene of the formula Hal in which Hal represents chlorineor bromine, and X and Y have the meanings stated above, is reacted withan aniline of the formula Z a w@ (In) in which Z and n have the meaningsstated above, in the presence of an acid-binding agent.

In the practice of the invention,

X stands preferably for hydrogen or nitro,

Y stands preferably for chlorine, bromine, CR, or nitro,

Z stands preferably for chlorine, bromine, fluorine, iodine,trifluoromethyl, nitro, cyano, for alkyl or alkylsulphonyl with, in eachcase, one to three carbon atoms, for cyclopentyl, cyclohexyl, dimethylamino, diethylamino or morpholino, and

n stands preferably for 0 to 3.

When n is greater than 1, Z may have different meanings.

The halonitrothiophenes of the formula (II) used as starting materialsare known and preparation takes place according to described oranalogous processes. (C. D. Hurd, K. L. Kreuz,J. Amer. Chem. Soc. 74,2965 [1952]; R. Mozingo et al., J. Amer. Chem. Soc. 67, 2092 [1945]).

The reaction may be carried out in the presence of a solvent which termincludes a mere diluent. All organic solvents are suitable. Theseinclude preferably polar solvents such as alcohols, for examplemethanol, ethanol and butanol, ketones, such as acetone, methylethylketone and diethyl ketone, acetonitrile, dimethyl formamide andnitromethane. The reaction can also be accomplished without diluents,the aniline of the formula (III) in fairly large excess then acting asdiluent.

As acid acceptor, preferably a further equivalent of the anilinederivative (lll) may be used. Depending on the basicity of the aniline,the appropriate amount of one of the customary tertiary amines, forexample triethylamine, dimethylaniline, mine, may also be used. Lessadvantageous are inorganic acid-binders such as alkali metal hydroxidesor alkali metal carbonates.

The reaction temperatures can be varied within a fairly wide range. Ingeneral, the reaction is carried out at 20 to 120, preferably 30 to C.

When carrying out the reaction according to the invention, 1 mole ofaniline derivative (Ill) and 1 mole of acid-binder may be used per moleof 2-halonitrothiophene of the formula (11). The acid-binder may bereplaced by a further mole of aniline. With a still larger excess ofaniline, the diluent may be dispensed with. Remarkably, in the casewhere, in formula (II), Y stands for chlorine or bromine, and Hallikewise stands for chlorine or bromine, the compound, even with anN,N-dimethylbenzylaexcess of the aniline (Ill), reacts to give only amonoanilino derivatives of the formula (I).

As already mentioned above, the new compounds are distinguished by anoutstanding insecticidal and acaricidal effectiveness. Moreover, theypossess only a slight toxicity to warm-blooded animals and only slightphytotoxicity. The pesticidal activity sets in rapidly and islong-lasting.

The new compounds are therefore used with success in crop protectionandthe protection of stored products, as well as in the hygiene field, forthe control of noxious sucking and biting insects, as well as mites.

To the sucking insects there belong, in the main, aphids (Aphidac) suchas the green peach aphid (Myzus persic'ae), the bean aphid (Dorulisfabue), the bird cherry aphid (Rlwpalosiplzzmz pzuli. the pea aphid(Mucmsip/ium pisi) and the potato aphid (Muc'rosip/ium .s'olun 'fblii),the currant gall aphid (Cryptomyzus km-sclwlzi), the mealy apple aphid(Sappuphix mall), the mealy plum aphid (H \'al0pleru.s' urundinis) andthe cherry black fly (Myzus ceras'i); in addition, scales and mealybugs(Coccina), for example the oleander scale (Aspidioms lzulerue) and thesoft scale (Lecanium liespcrizlum) as well as the grape mealybug(PM!(([OCUCL'US maritimus); thrips (Tliysunoptw'u), such asHereinallzripx femmzllis, and bugs, for example the beet bug Plasmaqumlrulu), the cotton bug (D \S(1(I'('ll.' intermezlius), the bed bug(Cimex learn/arias), the assassin bug (R/wzlnilm' prulixus) and Chagas'bug (Triummu [l festans) and, further, cicadas, such as Euscelishilolmlus and Nep/mretlix hipllHCfUlllS, and the like.

In the case of the biting insects, above all there should be mentionedcaterpillars (Lepidoptera) such as the diamond back moth (Plutellamuclllipemzl'x), the gypsy moth (Lymmzlriu dispar), the brown-tail moth(Euprm'lis c/zr \'s0rr/wea) and tent caterpillar (Maluc'usomurzeusrria); further, the cabbage moth (Mamesrra brusxicue) and thecutworm (Agrotis segemm), the large white butterfly (Pieris brassicue),the small winter moth (Clieimumbiu brumata), the green oak tortrix moth(Turtrix virizlana), the fall armyworm (Lzlpliygnw ji'ugiperdu) andcotton worm (Pm'zlenia litm'a), the ermine moth (Hypunmneuta padella),the Mediterranean flour moth (Eplzestiu kz'i/miella) and greater waxmoth (Galleria mellmiellu); and the like.

Also to be classed with the biting insects are beetles (Coleoptera), forexample the granary weevil (Silop/u'lus gramlrl'us Calandra grmuu'l'a),the Colorado beetle (Leprinotursu zlecemlineala), the dock beetle(Gastrop/zysu virizlula), the mustard bettles (Plzaezlon each/curiae),the blossom beetle (Meliget/ies aeneus), the raspberry beetle (Bymrusmmenmsus), the bean weevil (Bruc'lu'zlius Acan host's/ides ulJtec'tus),the leather beetle (Dermesles frisc'lzi), the khapra beetle (Trugodermugranarium), the flour beetle (Tribolium castaneum), the northern cornbillbug (Calandra or Sl'tophilus :eumul's), the drugstore beetle(Stegobium paniceum), the yellow mealworm (Tenelzrl'o molitur) and thesaw-toothed grain beetle ()ryzaeplzilus Surinamensis), and also speciesliving in the soil, for example wireworms (Agrz'otcs spec.) and larvaeof the cockchafer (Melolonrlzu melolont/za); cockroaches, such as theGerman cockroach (Blane/la germunicu); American cockroach (Periplanetaamericuna), Madeira cckroach (Lcucoplzaeu or Rliyparobia madeirae),Oriental cockroach (Blatta orientulz's), the giant cockroach (Blaheruxgiganteus) and the black giant cockroach (Blulierm'jilsc'us) as well asHensclzuutezlerziu flarivilta; further, Orthoptera, for example thehouse cricket (Ar/zeta dwnestic'us); termites such as the easternsubterranean termite (Reticulitermesflavipes) and Hymenoptera such asants, for example the garden ant (LlISlllS niger), and the like.

The Diptera comprise essentially the flies, such as the vinegar fly(Drusopliila melunogastcr), the Mediterranean fruit fly (Ceralitiscapitata), the house fly (Musca zlonmstica), the little house fly(Fannia cunicularis), the black blow fly (P/zormia aegina) andbluebottle fly (Calliplmra erytlzroceplala) as well as the stable fly(Stomoxys culcitmns); further, gnats, for example mosquitoes such as theyellow fever mosquito (Aedes aegypri), the northern house mosquito(Culex pipiens) and the malaria mosquito (Anopheles slep/zensi); and thelike.

With the mites (Acari) there are classed, in particular, the spidermites (Telmnycliizlue) such as the twospotted spider mite (Terranyc/umtelurius Terrarrvc'lzus ulrlzat'ae or Tetra/rvclzus urticzm) and theEuropean red mite (Paratclmnyc'llus pilusus Punonyc'lzus ulmi blistermites, for example the current blister mite (El-i0- ]7/I' \'LS ribis)and tarsonemids, for example the broad mite (Hemitursmzemus Imus) andthe cyclamen mite (Tarsmzemuis pal/Mus); finally, ticks, such as thereplapsing fever tick (Ornit/wdorus mouluita); and the like.

When applied against hygiene pests and pests of stored products,particularly flies and mosquitoes, the new compounds are alsodistinguished by an outstanding residual activity on wood and clay, aswell as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e., plant compatible or herbicidally inert)pesticide diluents or extenders, i.e., diluents or extenders of the typeusable in conventional pesticide formulations or compositions, e.g.conventional pesticide dispersible carrier vehicles such as solutions,emulsions, suspensions, emulsifiable concentrates, spray powders,pastes, soluble powders, dusting agents, granules, etc. These areprepared in known manner, for instance by extending the active compoundswith conventional pesticide dispersible liquid diluent carriers and/0rdispersible solid carriers optionally with the use of carrier vehicleassistants, e.g. conventional pesticide surface-active agents, includingemulsifying agents and/or dispersing agents, whereby, for example, inthe case where water is used as diluent, organic solvents may be addedas auxiliary solvents. The following may be chiefly considered for useas conventional carrier vehicles for this purpose: inert dispersibleliquid diluent carriers, including inert organic solvents, such asaromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.),halogenated, especially chlorinated, aromatic hydrocarbons (e.g.chlorobenzenes, etc.), parafflns (e.g. petroleum fractions), chlorinatedaliphatic hydrocarbons (e.g. methylene chloride, etc. alcohols (e.g.methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine,etc.), ethers, ether-alcohols, (e.g. glycol monomethyl ether, etc.),amides (e.g. dimethyl forrnamide, etc.), sulfoxides (e.g. dimethylsulfoxide, etc.), ketones (e.g. acetone, etc.) and/or water; as well asinert dispersible finely divided solid carriers, such as ground naturalminerals (e.g. kaolins, alumina, silica, chalk, i.e., calcium carbonate,talc, kieselghur, etc.) and ground synthetic minerals (elg. highlydispsersed silicic acid, silicates, e.g. alkali silicates, etc); whereasthe following may be chiefly considered for use as conventional carriervehicle assistants, e.g. surface-active agents, for this purpose:emulsifying agents, such as non-ionic and/or anionic emulsifying agents(e.g. polyethylene oxide esters of fatty acids, polyethylene oxideethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc, andespecially alkyl arylpolyglycol ethers, magnesium stearate, sodiumoleate, etc.); and/or dispersing agents, such as lignin, sulfite wasteliquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other acaricides andinsecticides, or rodenticides, fungicides, herbicides, bactericides,etc., if desired, or in the form of particular dosage preparations forspecific application made therefrom, such as solutions, emulsions,suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 01-95% by weight, andpreferably O.5907( by weight, of the mixture, whereas carriercomposition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about ().0005%, preferably0.005-57c, by weight of the mixture. Thus, the present inventioncontemplates over-all composi tions which comprise mixtures of aconventional dispersible carrier vehicle such as (l) a dispersible inertfinely divided carrier solid, and/or (2) a dispersible carrier liquidsuch as an inert organic solvent and/or water preferably including asurface-active effective amount ofa carrier vehicle assitant, eg. asurface-active agent, such as an emulsifying agent and/or a dispersingagent, and an amount of the active compound which is effective for thepurpose in question and which is generally between about 0,000595%, andpreferably 0.005-95%, by weight of the mixture.

The active compound can also be used in accordance with the well knownultra-low-volume process with good success, i.e., by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50-100 microns, oreven less, i.e., mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 1 quart/acre, preferably 2-16 fluidounces/acre, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about by weight of active compoundor even the active substance alone, e.g. about 20100% by weight of theactive compound.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. arthropods, i.e., insectsand acarids, and more particularly methods of combating at least one ofinsects and acarids which comprises applying to at least one ofcorrespondingly (a) such insects, (b) such acarids, and (c) thecorresponding habitat thereof, i.e., the locus to be protected, acorrespondingly combative or toxic amount, i.e., an arthropodicidally,especially insecticidally or acaricidally, effective amount of theparticular active compound of the invention alone or together with acarrier vehicle as noted above. The instant formulations or compositionsare applied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, squirting, sprinkling,pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particularnew compounds of the present invention are illustrated, withoutlimitation, by the following examples:

EXAMPLE 1 Plutella test (plantdamaging insects) Solvent: 3 parts byweight dimethyl formamide Emulsifier: 1 part by weight alkylarylpolyglycol ether To produce a suitable preparation of active com pound,1 part by weight of the active compound is mixed with the stated amountof solvent containing the stated amount of emulsifier and theconcentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation ofthe active compound until dew moist and are then infested withcaterpillars of the diamondback moth (Plutella maculipennis),

After the specified periods of time, the degree of destruction isdetermined as a percentage: 100% means that all the caterpillars arekilled whereas 0% means that none of the caterpillars are killed.

The active compounds, the concentrations of the active compounds, theevaluation times and the results can be seen from the following Table 1.

Tablel (plant-damaging insects) Plucella test Active compoundsConcentration Degrce of destrucof active tion in 7. after compound in Z3 days (lmown) C n 80 I 0.2 0

(known) 2 0 u Qna 0 2 100 2 p 0:02

l 0.2 100 (a) 0 H 0.02 100 1 0.002 100 s o n id 0.2 100 Cl 0.02

7 c n un 01 0.2 0.02 100 Plucella tea I:

concentration Active compounds Degree of destrucof active tion in 7.after compound in Z 3 days I 1 (8) 0.2 100 c n Q n 0.02 100 2 OF 10 0.2100 c n dud 0.02

02 cr I 3 0. 2 11) 0.02 Q 0.002 a0 EXAMPLE 2 Cabbage leaves (BI'USSiLlIoleracea) are sprayed with Phaedon larvae test (plant-damaging insects)Solvent: 3 parts by weight dimethyl formamide Emulsifier: 1 part byweight alkylaryl polyglycol.

ether To produce a suitable preparation of active compound, 1 part byweight of the active compound is mixed with the stated amount of solventcontaining the stated amount of emulsifier, and the concentrate isdiluted with water to the desired concentration.

the preparation of the active compound until dripping wet and theninfested with mustard beetle larvae (Phaedun (och/curiae After thespecified periods of time, the degree of destruction is determined as apercentage: l00% means that all the beetle larvae are killed. 0% meansthat none of the beetle larvae are killed.

The active compounds, the concentration of the active compound, thetimes of evaluation and the results can be seen from the following Table2.

Table 2 (plant-dar aging insects) Phaedun larvae test Concentration cams)2 Active compounds Degree of descrhcof active tion in 74 after compoundin 7. 3 days B S Br (known) (known) 1a 0 n 0.2 100 2 H 0.02 so -v 08(03)2 (19,) O 0.2 100 2 0.02 so EXAMPLE 3 Tetranychus test (plant-damagingmites) Solvent: 3 parts by weight dimethyl formamide Emulsifier: 1 partby Weight alkylaryl polyglycol ether To produce a suitable preparationof active compound, 1 part by weight of the active compound is mixedwith the stated amount of solvent containing the stated amount ofemulsifier and the concentrate so obtained is diluted with water to thedesired concentration.

Bean plants (Phaseolus vulgaris), which have a height of approximately10-30 cm., are sprayed with the preparation of the active compound untildripping wet. These bean plants are heavily infested with spider mites(Tetra/13172115 urtic'uc) in all stages of development.

After the specified periods of time, the effectiveness of thepreparation of active compound is determined by counting the dead mites.The degree of destruction thus obtained is expressed as a percentage:10071 means that all the spider mites are killed whereas means that noneof the spider mites are killed.

The active compounds, the concentrations of the active compounds, theevaluation times and the results can be seen from the following Table 3.

Table 3 (plantdamaging mites) 'letran chus test The following furtherexamples are set forth to illustrate, without limitation, the processfor producing the active compounds according to the present invention.

EXAMPLE 4 H0 1 l (1) 5 2G 8.4 g (0.04 mole) of2-chloro-3,S-dinitrothiophene are dissolved in 160 ml of ethanol, withheating. A solution of 10.3 g (0.08 mole) of 4-chloroani1ine in ethanolis then added dropwise and the mixture is heated under reflux for 1.5hours. Suction filtration of the yellow precipitate formed issubsequently effected; the product is washed with water and ethanol anddried. There are obtained 12 g (95% of the theory) of 2-(4'-chloroanilino)-3,S-dinitrothiophene of melting point 17l177C(recrystallized from a little acetone: melting point 177C).

Degree of des true- Active compounds concentration of active tion in Zafter compound in 1 2 days (known) i r o n a 0.2 100 2 s 0.02 20 EXAMPLEEXAMPLE 6 12.7 g (0.05 mole) of 2bromo3,S-dinitrothiophene and 19.6 g(0.1 mole) of 3-ch1oro-4- trifluoromethylaniline are dissolved in 200 mlof nbutanol and heated under reflux for 7 hours. After cooling, the paleyellow precipitate is filtered off with suction, washed with water andevaporated to dryness in a little hot ethanol; there are then obtained14 g (76% of the theory) of 2-( 3 -chloro-4'-trifluor0methylanilino)-3,S-dinitrothiophene of melto n s (a) ing point154C.

EXAMPLE 7 I 0 S n I 3 20.8 g (0.1 mole) of 2-chloro-3,S-dinitrothiopheneare suspended in 91.6 g (0.4 mole) of 3,5-bistrifluoromethylaniline andheated to 90 to 100C for hours. After cooling, the oily residue is takenup in ether, the excess aniline is precipitated with hydrochloric acid,suction filtration is effected and the filtrate is concentrated byevaporation. The residue is recrystallized from propanol. There areobtained 24 g (60% of the theory) of2-(3,5-bistrifluoromethylanilino)-3,5- dinitrothiophene of melting point98-101C.

EXAMPLE 8 s n 01 c n Q- 25.3 g (0.1 mole) of2-bromo-3,S-dinitrothiophene together with 16.2 g of 3,4-dichloroanilineare dissolved in 250 ml ethanol; 12.1 g of N,N-dimethylaniline are addeddropwise at boiling temperature and stirring is subsequently effectedfor 1 hour at to C. After cooling the precipitated product is washedwith water, and recrystallized from acetone. 25 g (75% of the theory) of2-(3,4-dich1oroanilino)-3,5-dinitrothiophene of melting point 193C areobtained.

Preparation of the starting product 2-bromo-3,5-dinitrothiophene:

782 g 2-bromothiophene are added dropwise over 3 hours, at 0 to 10C, toa nitrating mixture consisting of 3.85 l of 9871-St1811gtl'1 nitricacid, 9 l sulphuric acid and 3 l oleum (containing 20% sulphurtrioxide), and stirring is subsequently effected for 12 hours at 0C. Themixture is then decomposed with 30 kg of ice; the precipitated,deep-yellow product is filtered off with suetion, dried in a vacuum at40C and recrystallized from alcohol. 494 g of2-bromo-3,S-dinitrothiophene of melting point 132C are obtained.

EXAMPLE 9-43 The compounds of the following further Examples wereprepared in corresponding manner. The Table identifies the radicals setout in formula (1).

Example No. X Y Z n mp. C

9 H NO. 2-C1 1 182-183 10 H NO 2,6(CH;,) 2 152 1 1 H NO. 4--SO. ,CH 1201-202 12 H N0 4-NO 1 208-210 13 H N0 2,3C1 2 183-184 14 H NO: 2.5Cl 2163 15 H NO: 2,4C1 2 163 16 H NO: 2,6-Cl 2 153 18 H NO 2,6-(CH(CH;,) 2181 19 H N0 4- N 0 1 252 20 H NO 3,5C1 2 172-173 21 H N0 4N(CH;,) 1 19322 H NO. 3,4,5C1 3 207 24 H NO: 2,4,5-Cl; 3 158-161 25 H NO: 2Cl, 5CF; 2103 27 N0 Br 2,6(C H 2 146 28 N0 C1 4,5-C1 2 151 29 N0 Cl 2CH;1. 5NO. 2138 30 N0 Br 4.5C1- 2 129-132 31 N0 C1 2,6(C H 4-CH 3 159 33 NO C12CH;,. 4 2 143 35 NO: Br 4NO 1 171 36 NO: Br 4C1 1 37 NO: Cl 2-C1 1134-135 38 N0 131' 2,6(CH; 2

39 NO: Br 3CF 1 143-151 40 NO: Br 3,5-(CF; 2 157-158 41 NO: C13,5-(CF3)- 2 159-160 42 N0 C1 3(1"';, 1 131-132 43 N0 Br 2,4,5(1;, 3 114-1 16 It will be realized that all of the foregoing compoundscontemplated by the present invention possess the desired selectivepesticidal, especially arthropodicidal, i.e. insecticidal or acaricidal,properties for combating insects and acarids, and that such compoundshave a lowphytotoxicity and a-correspondingly low mammas lian toxicity.

As'may be used herein. the terms arthropoi:l arthropodicidal andarthropodicide contemplate spe= cificallyboth insects and acarids. Thus,the insects and acarids may be considered herein collectively asarthropods to be combated in accordance with the invention, andaccordingly the insecticidal and/or acaricidal activity may be termedarthropodicical activity, and the concomitant combative or effectiveamount used will be an arthropodicidally effective amount which ineffect means an insecticidally or acaricidally effective amount of theactive compound for the desired purposes It will be appreciated that theinstant specification and examples are set forth by way of illustrationand not limitation, and that various modifications and changes may bemade without departing from the spirit and scope of the presentinvention.

What is claimed is:

l. A method of combating insects or acarids which comprises applying tothe insects or acarids an insecticidally or acaricidally effectiveamount of a compound of the formula in which X represents hydrogen ornitro,

Y represents halogen, trifluoromethyl or nitro,

Z represents halogen, cyano, nitro, lower alkyl, halolower alkyl, loweralkoxy, lower alkylthio, lower alkylsulphinyl, lower alkylsulphonyl,cycloalkyl, dialkylamino wherein each alkyl group contains up to sixcarbon atoms or amino wherein the nitrogen is part of a saturatedheterocyclic ring, and

n is an integer from O to 3.

2. The method according to claim 1 in which X stands for hydrogen ornitro, Y stands for chlorine, bromine, trifluoromethyl, or nitro, Zstands for chlorine, bromine, fluorine, trifluoromethyl, nitro, cyano,alkyl or alkylsulphonyl with one to three carbon atoms, cyclohexyl,dimethylamino, diethylamino or morpholino.

3. The method according to claim 1 wherein such compound is 2-(3',4-dichloroanilino)3,5-dinitrothiophene 0f the formula v 4. The methodaccording to claim 1 wherein such compound is2-(3',5dichloroanilino)3,5-dinitrothio phene of the formula 5. Themethod according to claim 1 wherein such compound is2-(2,4,5'trichloroanilino)-3,5-dinitrothiophenc of the formula 0 H NH 01H 6. The method according to claim 1 wherein such compound is2-(3-chloro-4'-trifluoromethylanilino)- 3,5-dinitrothiophene of theformula 0 11 NH Cl? 7. The method according to claim 1 wherein suchcompound is 2-(2'-chloro-5-trifluoromethylanilino)- 3,5-dinitrothiopheneof the formula 8. The method according to claim 1 wherein such 6compound is 2-(3,5'-di-trifluoromethylanilino)-3,5-

dinitrothiophene of the formula 9. The method according to claim 1wherein such compound is 2-(4-chloroanilino)-3,S-dinitrothiophene of theformula 10. An insecticidal or acaricidal composition com prising aninsecticidally or acaricidally effective 55 amount of a compound of theformula 2O phcn. 2-( 2',4',5'-trichlorounilino )-3,5-dinitr0thiophene,2-( 3 '-chlor0-4'-trifluoromethylanilino )-3 5- dinitro'thiophene, 2-( 2-chloro-5 trifluoromcthylanilino)-3.5-dinitrothiophene, 2-(3,5-di-trifluoromethylanilino)-3,5-dinitrothiophene or 2- 4 -chl0roanilin0)-3 ,5-dinitrothiophene.

1. A MEHTOD OF COMBINATING INSECTS OR ACARIDS WHICH COMPRISES APPLYINGTO TE INSECTS OR ACARIDS AN INSECTICIDALLY OR ACARICIDALLY EFFECTIVEAMOUNT OF A COMPOUND OF THE FORMULA
 2. The method according to claim 1in which X stands for hydrogen or nitro, Y stands for chlorine, bromine,trifluoromethyl, or nitro, Z stands for chlorine, bromine, fluorine,trifluoromethyl, nitro, cyano, alkyl or alkylsulphonyl with one to threecarbon atoms, cyclohexyl, dimethylamino, diethylamino or morpholino. 3.The method according to claim 1 wherein such compound is2-(3'',4''-dichloroanilino)-3,5-dinitrothiophene of the formula
 4. Themethod according to claim 1 wherein such compound is2-(3'',5''-dichloroanilino)-3,5-dinitrothiophene of the formula
 5. Themethod according to claim 1 wherein such compound is2-(2'',4'',5''-trichloroanilino)-3,5-dinitrothiophene of the formula 6.The method according to claim 1 wherein such compound is2-(3''-chloro-4''-trifluoromethylanilino)-3,5-dinitrothiophene of theformula
 7. The method according to claim 1 wherein such compound is2-(2''-chloro-5''-trifluoromethylanilino)-3,5-dinitrothiophene of theformula
 8. The method according to claim 1 wherein such compound is2-(3'',5''-di-trifluoromethylanilino)-3,5-dinitrothiophene of theformula
 9. The method according to claim 1 wherein such compound is2-(4''-chloroanilino)-3,5-dinitRothiophene of the formula
 10. Aninsecticidal or acaricidal composition comprising an insecticidally oracaricidally effective amount of a compound of the formula
 11. Acomposition according to claim 10 wherein said compound is2-(3'',4''-dichloroanilino)-3,5-dinitrothiophene,2-(3'',5''-dichloroanilino)-3,5-dinitrothiophene,2-(2'',4'',5''-trichloroanilino)-3,5-dinitrothiophene,2-(3''-chloro-4''-trifluoromethylanilino)-3,5-dinitrothiophene,2-(2''-chloro-5''-trifluoromethylanilino)-3,5-dinitrothiophene,2-(3'',5''-di-trifluoromethylanilino)-3,5-dinitrothiophene or2-(4''-chloroanilino)-3,5-dinitrothiophene.